A crystal of a different color

Chemists have unexpectedly made two differently colored crystals – one orange, the other blue – from one chemical in the same flask while studying a special kind of molecular connection called an agostic bond. The discovery, reported in Angewandte Chemie International Edition on July 29, is providing new insights into important industrial chemical reactions such as those that occur while making plastics and fuels.

One flask of chemicals gives rise to either blue or orange crystals. Credit: van der Eide/PNNL

"We were studying agostic bonds in a project to make liquid fuels like methanol from carbon dioxide to replace fuels we get from oil," said chemist Morris Bullock at the Department of Energy's Pacific Northwest National Laboratory. "We knew the molecule we were making would have an agostic bond, but we had no idea there'd be two flavors of these metal complexes."

While chemists have studied these bonds in chemicals in liquid form, no one had crystallized one chemical with multiple forms of its agostic bonds. And no one expected different forms to give rise to different colors.

Bonds come in many varieties in molecules. They string atoms together, sometimes forming a trunk and branches of atoms like a tree. But the trunk and branches of chemicals often fold up into a more compact shape, requiring additional weaker bonds to hold the shape in place. An agostic bond is one of these additional bonds, a shape-holder. They occur between a metal and a distant carbon-hydrogen bond along some chain, folding the chain back to the metal and pinning it there.

First discovered in the 1980s, agostic bonds frequently occur in catalysts because catalysts usually contain metals. This work will help researchers get a better handle on some catalytic reactions found in common industrial processes such as making plastic or fuels.

Heart of the Matter

The metal in a catalyst is usually the reactive heart of the molecule. Bullock and postdoctoral chemist Edwin van der Eide knew an agostic bond in their catalyst would help protect the reactive metal from working at the wrong time: The carbon-hydrogen bond blocks the reactive metal until conditions were right, which in turn would help the scientists better control the catalytic reactions. So van der Eide set about producing and crystallizing catalysts that contain a metal atom -- in this case, molybdenum.

In the lab, van der Eide's flask of chemicals held a molybdenum-containing molecule that turned the solution violet. He added another liquid to coax the molybdenum complex to crystallize, just as salt crystallizes from seawater to form flakes at the seashore. Some crystals formed at the bottom of the flask and others formed near the top of the violet solution.

Oddly, the crystals were two different colors.

Orange crystals formed at the bottom of the flask and blue above. If van der Eide dissolved either the orange or blue crystals in a fresh flask of the original solvent, the violet color returned, with the same properties as the original violet solution. These results suggested that either molecule in the two colored solids could give rise to both structures in liquid, where they easily change back and forth.

The researchers examined the differently colored crystals to determine their structures. The molecule forms a shape like a piano stool: a ringed section forms a stool seat on top of the molybdenum atom, with multiple legs connecting to the molybdenum at the bottom.

One of the legs, however, is longer than the others and contains a chain of three carbon atoms, each with at least one protruding hydrogen. The team found that the long leg was involved in the agostic bonds, with the middle carbon atom involved in the orange crystals and an end carbon involved in the blue crystals.

PNNL's Ping Yang at EMSL, DOE's Environmental Molecular Sciences Laboratory on the PNNL campus, took to EMSL's supercomputer Chinook to perform theoretical calculations on the orange and blue structures. Chemically, the two structures were almost equally likely to form, with the blue one having a slight edge. The analysis also revealed why the crystals were different colors, which is due to subtleties within the structures.

This work was supported by the Department of Energy, Office of Science.

The Department of Energy's Office of Science is the single largest supporter of basic research in the physical sciences in the United States and is working to address some of the most pressing challenges of our time. For more information, please visit http://science.energy.gov/.

Interdisciplinary teams at Pacific Northwest National Laboratory address many of America's most pressing issues in energy, the environment and national security through advances in basic and applied science. Founded in 1965, PNNL employs 4,400 staff and has an annual budget of more than $1 billion. It is managed by Battelle for the U.S. Department of Energy. For more information, visit the PNNL News Center, or follow PNNL on Facebook, LinkedIn and Twitter.

EMSL, the Environmental Molecular Sciences Laboratory, is a national scientific user facility sponsored by the Department of Energy's Office of Science. Located at Pacific Northwest National Laboratory in Richland, Wash., EMSL offers an open, collaborative environment for scientific discovery to researchers around the world. Its integrated computational and experimental resources enable researchers to realize important scientific insights and create new technologies. Follow EMSL on Facebook, LinkedIn and Twitter.

Die letzten 5 Focus-News des innovations-reports im Überblick:

Physicists of the University of Würzburg have made an astonishing discovery in a specific type of topological insulators. The effect is due to the structure of the materials used. The researchers have now published their work in the journal Science.

Topological insulators are currently the hot topic in physics according to the newspaper Neue Zürcher Zeitung. Only a few weeks ago, their importance was...

In recent years, lasers with ultrashort pulses (USP) down to the femtosecond range have become established on an industrial scale. They could advance some applications with the much-lauded “cold ablation” – if that meant they would then achieve more throughput. A new generation of process engineering that will address this issue in particular will be discussed at the “4th UKP Workshop – Ultrafast Laser Technology” in April 2017.

Even back in the 1990s, scientists were comparing materials processing with nanosecond, picosecond and femtosesecond pulses. The result was surprising:...

A multi-institutional research collaboration has created a novel approach for fabricating three-dimensional micro-optics through the shape-defined formation of porous silicon (PSi), with broad impacts in integrated optoelectronics, imaging, and photovoltaics.

Working with colleagues at Stanford and The Dow Chemical Company, researchers at the University of Illinois at Urbana-Champaign fabricated 3-D birefringent...

In experiments with magnetic atoms conducted at extremely low temperatures, scientists have demonstrated a unique phase of matter: The atoms form a new type of quantum liquid or quantum droplet state. These so called quantum droplets may preserve their form in absence of external confinement because of quantum effects. The joint team of experimental physicists from Innsbruck and theoretical physicists from Hannover report on their findings in the journal Physical Review X.

“Our Quantum droplets are in the gas phase but they still drop like a rock,” explains experimental physicist Francesca Ferlaino when talking about the...